DE1936494A1 - insecticides - Google Patents

Description

PATENT LAWYERS
DR. -ING. H. FINCKE DIPL.-ING. H. BOHR DIPL..ING. S. STAEGER

For r η r u f: »26 ίΟίΟ

θ MUNICH S, MOIIerstrae «3)

«" 1936494 1 7. JUL119 (59

Folder 8119 - Dr ₀ K.

COMOHWEALTH SCIENTIFIC AND INDUSTHIAl RSSBARCH ORGANIZATION, East Melbourne, Victoria, Australia

insecticides

Priority: 17th July 1968 - Australia

The invention relates to new insecticidal compounds and to insecticidal compositions, and to methods of making the same. The invention also relates to new ones synthetic procedures for the new and related compounds

The new compounds proposed according to the invention have the general formula I.

OCH,

where η is 0 or 1.

909884/1798

The connections are therefore ea

(a) 1,1-bis (p-ethoxyphenyl) -2,2-dimethylpropane and

(b) 1,1 -Bis (p-ethoxyphenyl) -3 , 3-dimethyl-n-butano

(These connections are hereinafter collectively referred to as the "connections I "and individually as the" Connection Ia "and the" Connection Ib ".)

Me compounds Ia and Ib are valuable insecticides and are active against DDT-resistant insect _{strains o} In addition, genetic pressure tests of the compounds against laboratory strains have no resistance to skin flies. The compounds can also be potentiated to activity values that match those of DDT are comparable.

The compounds have an extremely low acute toxicity to mammals and, since they do not contain halogen, they do not give rise to any residue problems such as occur with halogenated insecticides be encountered.

Compounds related to compounds I are known. In particular, the corresponding p-methyl and p-methoxy compounds have been described by E. F ₀ Rogers and HD »Brown in one or more of the following references;

(1) Joraal of the American Chemical Society, Volume 75, Page 2991

(1953h

(2) Ibid, Vol. 72, page 1864 (1950);

(3) üoS patent 2 682 561 ο

The unsubstituted phenyl analogue of the compound Ia and its halogenated derivatives have also been reported by Rogers and Brown in

(4) U »So Patent 2,641,617 and

(5) UoS _e Patent 2 641 618 -.

909884/1798

described ,,

Rogers and Brown state that the p-methoxy analog of compound Ib (d "ho" dianisylneohexane * ¹ ) has no insecticidal activity, but they claim that the p- _{methoxy analog of compound Ia (d e} h _o "dianieylneopentane") does They find that the LDcrt of the latter compound in mosquito larvae (Aedes aegypti) is twice that of methoxychlor, and in house flies it is four times that of methoxychlor. 'However, later determinations by others show People that dianisylneopentane is only about 0.08 times as active against house flies as methoxychlor (See "Organic Insecticides" RoL * Metcalf, Interscience Publishers Inc., 1955 at page 145) o Rogers and Brown (Reference 2) also note that house flies resistant to DDT show a marked resistance to dianisylneopentane <>

Because of the numerous changes in testing procedures and the Species and strains of insects used to obtain the activity numbers given in earlier references and because of a general increase in the resistance of many insect species to DDT and related ones Insecticide has taken place since the older experimental data specified, it is difficult to poison a public dare to make the activity of new insecticidal compounds with those of the prior art. Accordingly, the activities a number of known insecticides are again determined for a given insect strain by the methods described in the examples for the determination of the activities of the new ver bindings are indicated,

909884/1798

Table I compares the activities of a number of "known insecticides" determined in this way with those of the compounds I against house flies (Mueca domeetica) and yellow fever mosquito larvae (Aedes aegypti) (both respond to DDT) _{or the like}

Table I. link ^LD 50 ^L0 100 (Medomestica) 1,1 -Bis (p-chlorophenyl) ~ 2p2,2-
trichloroethane (DDT) 0.26 0.15 1,1 -Bis (p-methoxyphenyl) -2,2,2 ~
trichloroethane (methoxychlor) 0.33 0.25 1,1-bis (p-ethoxypheny1) -2,2,2-
trichloroethane 0.31 0.08 1,1 -Bis (p-ae thoxyphenyl) -2,2,2-
dimethylpropane (dianisylneopentane) 5.2 0.625 * Connection Ia 1.92 0.32 Connection Ib 2.0 0.5

Taken from reference (3) by Rogers and Brown _o

From the numbers in Table I it can be seen that dianisylneopentane about 0.06 times the activity of methoxychlor, whereas .the compound I about 0.16 to 0.17 times Possesses activity of Hethoxychlor (determined against house flies),

Obviously, the compounds I have not yet been described, nor has their insecticidal activity been specified or from known theories about the insecticidal structures and activity relationships predicted ο If also the activity schedule of methoxychlor and its ethoxy analog by reference

909884/1798

on dianieylneopentane and the compound Ia are considered is, then it is to be expected that the compound Ia can be expected at most an activity, which in the best case with that of Dianieylneopentan tu compare is «. It is therefore surprising if it is found that compound Ia has more than 2.5 times the activity of dianisylneopentane »this activity is even more surprising when one considers that the next members of the series, for example those compounds with n- or iso-propoxy substituents in the aromatic rings as insecticides are inactive.

The activity of the compound Ib is completely unexpected since dianisylneohexane is completely inactive as an insecticide

Furthermore, the ethoxy-substituted compounds can be unequal their analogues with halogen substituents in the aromatic rings, against insecticide-sensitive and. insectiaid resistant Species of insects are potentiated to a degree that so far has not been observed with the general types of insecticidesο this potentiieruhg can reduce the activity of the new Economically increasing compounds against some of the major hardy species of insects

The invention also relates to method xu? Making the new Compounds and certain known related compounds, some of which have been mentioned above. According to the procedures of the The state of the art for the production of the known preliminary compounds is a compound of the formula II

909884/1798

II

wherein R is a hydrogen atom or a methyl or methoxy group means and X means OH, with hydrogen and a copper chromite catalyst at about 420 kg / cm and 250 ° C. several Hours reduced (Rogers and Brown reference. (3) »(4), (5)). Compounds I can be prepared by such a method but if the product is not carefully cleaned to remove traces of the garbinol, the latter will work as an inhibitor of the insecticidal action of the end productSo It has now been found that the reduction is more effective with sodium can be carried out in liquid ammonia «. The complicated and expensive high-pressure hydrogen reduction can thus be abandoned "It's a surprising plague that sodium is in liquid ammonia reduces an alcohol, which in addition is still sterically hindered »The reduction can be done with compounds of formula II, in which R is a lower alkyl or alkoxy group »

(The terms "lower alkyl" and "lower alkoxy" such as they are used here denote alkyl and alkoxy groups that contain 1 to 6 carbon atoms »)

According to the invention, Sa is furthermore a method of production of compounds of the general formula Ha

179-8-

beat

H
C.
(CH ₂ ) n

Ha

OH,

wherein η is 0 or 3 and R is hydrogen, .. lower.Alkyl or lower alkoxy ", which is carried out by" that a compound of the formula IIT>

(CH ₂ ) n

CH.

CTI . f% ___

ΧΙ— ■ "" V / '"in ■■■ ·« · ■

J 2

CH ₃

wherein η is 0 or 1 and R is hydrogen, lower alkyl or lower alkoxy means reduced with sodium in liquid ammoniao

The compounds of formula Hb can be prepared by any suitable standard method, for example by reacting 2 moles of the corresponding Grignard dervate of the phenyl moiety with 1 mole of a lower alkyl ester or acid halide of 2 _S 2-dimethylpropanoic acid (for compounds in

909884/17 98

■ - 8 -

where η is O) or of 3,3-dimethyl-1-butanoic acid (for compounds in which η is 1) _o

PIe general procedures for performing reductions with Sodium in liquid ammonia (Birch reduction) are well known and need not be described further, with the exception of if you focus on the manufacture of the special inventive Relate connections.

Me compounds I of the present invention and the homologues the same can also be produced according to a further feature of the invention by a method carried out thereby is that an aldehyde of the formula III

(CH ₂ ) -CH = O III

where η is O or 1, or a reactive .Derivat same, with a compound of formula IV

-ι

QR " ^v
. ι

IV

wherein R "is hydrogen or lower alkyl, in the presence of an acid or a Lewis acid ₀ when R" is hydrogen, then the product according to the formula Ha, wherein R ⁹ is lower alkyl, by alkylation of the starting product by

909884/1798

Standard methods, for example with a dialkyl sulfate, can be obtained Carbinol product (for example Formula III »above) not formed.

In this case, in the following embodiments of the method the reactants are preferably in near equimolar amounts are used. The acid or Lewis acid can in amounts ranging from catalytic amounts to solvent amounts be used.

Preferably, the bisulfite addition compound of the aldehyde III is used, but the free aldehyde or other reactive derivatives such as _0, the acetal can also be used "The reaction is preferably carried out in a mixture of concentrated sulfuric acid and acetic acid., Mchtoxydierende acids, such as _o B _o phosphoric acid, can be used just as well as Lewis acids, e.g. BP, _β «

According to a special feature, the invention relates to a process for the synthesis of 1 _t 1-bis (p-ethoxyphenyl) -2,2-dimethylpropane, which is carried out by mixing the pivalaldehyde / sodium bisulfite complex with phenol in a mixture of concentrated sulfuric acid and acetic acid and the resulting product is alkylated with diethyl sulfate «

According to a further special feature there is 1,1-bis (p-ethoxyphenyl) -2,2-dimethylpropane directly through "implementation of the pivalaldehyde / sodium bisulfite complex “With phenetol in a misuse. synthesized from concentrated sulfuric acid and acetic acid «.

According to a further special feature, 1,1-bis (p-ethoxyphenyl) -3,3-dimethylbutane is used synthesized by the 3,3-dimethyl

909884/1798

butyraldehyde / Hatriuebisulflt complex for the pivalaldehyde complex replaced in the two immediately preceding embodiments will"

As mentioned above, the compounds I described above are effective against insect pests, such as, for example, »flies, mosquitoes» hotts, Beetles and others, effective »

The compounds I can in a suitable inert solvent or solvent mixture or in a solid mixture which can be incorporated, although other substances, such as _o B "wetting agents, dispersants and adhesives incorporated are" The compounds can in such compositions either as the sole toxic agent or are useful in combination with other insecticides such as Z ₉ are as pyrethrum, rotenone, or heavy metal salts, or used with fungicidal or bactericidal agents, to provide compositions produce, agricultural for budgetary and dusting powders and sprays as well as for textile coating and -imprägnierung and the like. The compounds can be dissolved in suitable organic solvents in order to produce solutions with an improved effect. »The new compounds can also be incorporated into aqueous suspensions by dispersing compounds dissolved in organic solvents in water. finely divided, solid diluents or carriers, such as "Bo bentonite, sealing earth, talc, charcoal, pumice stone, calcium

. . ,, _. be mixed. _ carbonate and the like. The insecticidal compounds can be mixed in their original form or in solution «,

In particular, the compounds according to the invention can be used in are advantageously combined with other substances,

909884/1798

which have a synergistic or potentiating effect · In general, such substances prevent the setoxification of insecticides in insects, which is caused by the action of oxidative enzymes · Typical substances of this type are the Fyrethrlnsynergiete, vie 2.B ₀ Piperonylbutoiyd, Piperonylcyclonen, "Seeoxane" , "Sesamex", "sulfoxide", n-propyl isome and sesamine oil extracts _o It has been found that the substance "Sesoxane" (manufactured by Shulton Inc., Clifton, N ₀ J ₀ , USA) is particularly effective as a potentiator for the compounds according to the invention and can be used in amounts from about one thousandth to two times the weight of the compound, with the preferred range being from about one hundredth to the same amount by weight <>("Seeoxane" is 2- (3,4-methylenedioxyphenoxy) -3.6 , 9-trioxaundecane) _o

The preparation of the compounds I and the new chemical Intermediate products obtained during the course of the reaction are entered in the following examples, however it should be noted that these examples are only intended to illustrate the process which is used to prepare these compounds is used and that they are not to be construed in a limiting sense

example 1

Production of 1.1-bis (p-ethoxyphenyl) -2.2-dimeth.vlproi) on .

. (a) 60.3 g of p-bromophenetol was converted to the corresponding Grignard reagent by reaction with 7.3 g of magnesium in dry ether or tetrahydrofuran using standard procedures. _o To the cooled ether solution, 19.5 g of ethyl pivalate was added with stirring. After working up in

90988A / 1798

the ordinary Veise with Asstoniusichlorld and Wasohen was extracted dl · XtbtrlBsung, whereby the product 1 _t 1-bis (p * thoxyphenyl) was obtained -2,2-diaethylpropan-1-ol, which then ·· "■ was crystallized. Mp 81 ⁰ C; Yield 31.1g (63 Jt).

(b) 1.0 g (0.003 mol) of 1,1-bis (p-ethoxyphenyl) was dissolved in 15 ml of petroleum ether (b.p. 60 to 80 ⁰ C) -2,2-dimethjrlpropan-1-ol, and the resultant solution was added with stirring to a solution of 0.42 g (0.018 gram atom ^ S 80 al liquid tomonislr. The mixture was then left to stand for 2 hours, during which the asaonium evaporated was "extracted from 60 to 80 ⁰ C) the petroleum ether extract was washed several times with water and then evaporated to dryness to give 0.8 g of a product bit a melting point of 56 ⁰ C obtained ,, Two ümkristallisationen of the product from petroleum ether (60 to 80 ⁰ C) gave 1,1-bis (p-athoxyphenyl) -2,2- ^ dimethyl propane (formula I; η «0); mp 72 ⁰ C; yield 0.65 g (68 #).

The infrared spectrum of the product showed no absorption at 3650 Cm ^-1 O (OH)

The HMR spectrum was measured on a "Varian 60" spectrometer in Carbon tetrachloride using tetramethylsllane as

internal standard determined. The following maxima were found found:

<5 (pp « _e )« 0.98 (S; 9H): 1.37 (t; 6H): 3.53 (S; IH): 3.93 (q; 4H): 6.94 (m; 8H): (s * singlet; t = triplet; q »quartet m m MuI tipi et) _o

Gefunaeni C 80.3%; H 9 »2% i Theoretical value for C ₂₁ H ₂ .O _e : C βθ.7 \ z H i, n%,

90 9884/1798

Ma ··· j foundί H ⁺ - 312
Theory: H ⁺ * 3X2

(determined on a Hltaohl Ferkln bucket RMU-öD-Maeeenepectrometer)

BelBPiel 2

Production τοη 1.1 -BIb (p-ethoxyphenyl) -3.3-dineth.vlbutane .

(a) 20.1 g of p-bromophenetol were converted into the corresponding Grignard reagent by reacting 2.4 g of magnesium in 100 ml of dry diethyl ether using standard procedures. A solution of 7.1 g of ethyl neopentanoate was added to the cooled Grignard solution after the mixture had been refluxed for 4 hours and worked up and washed in the usual way with saturated ammonium chloride solution, the ether solution was evaporated off, the product 1,1-bis (p-ethoxyphenyl) -3i3 dimethylbutane-1 oil was obtained. Yield 31 ti g (63 %)

(b) 1.6 g (0.005 mol) of 1,1-bis (p-ethoxyphenyl) -3,3-dimethyl-butan-1-ol were dissolved in 40 ml of petroleum ether (b.p. 60 to 80 ⁰ C), and the resulting solution was added with stirring to a solution of 2 g (0.081 gram atom) of sodium in 60 ml of liquid ammonia. The mixture was then left to stand for several hours, during which time the ammonia evaporated. " The residue was decomposed with aqueous ammonium chloride and the resulting solution was extracted with petroleum ether (b.p. 60 to 80 ⁰ C) of the petroleum ether extract was washed several times with water and then but dryness to give a product which was purified from petroleum ether (30 to 60 ⁰ C) was crystallized, with 1,1-bis ^ (p-ethoxyphenyl) -2i, 3Hiimethylbutan (formula

9098 84/179

I; η - 1, H - OC ₂ H ₅ ) was cooled . Pp 54 ⁰ C $ Attebeut · 0.7%

The HMR spectrum was recorded on "Ines" Tarlan 60 "-3p" ktrc "" ter In Carbon tetrachloride using τοη Tetra »« thyleilan al · inner standard shrouded. The following maxiaa were found:

S (ppBo) »0.98 (β; 9H): 1.1 (d; 2H): 1.36 (t; 6H) ι 3.9 (.; 5H): 6.9 (m; 8H)

s = * Singuletj d »Pöblet; t * triplet; m »Multipleto analysis: Found: C 80.7 #JH 9.1 ßi 0 9 _t 9 %

Wept for C ₂₁ H ₂₉ P ₂ : C 81.0%} H 9.2% i 0 t,

Mass: found: M = 326 Iheory: M ⁺ »326

Example 3

1.1 -Bis (p-ethoxyphenyl) -2.2-dimethylpropane ,

8.7 g of pivalaldehyde / sodium bisulfite complex were added to 1-00 ml of a cold mixture (1: 1) of concentrated sulfuric acid and acetic acid, phenetol was slowly added and the reaction mixture was ^{stirred at 0 to 5 °} C. for 3 hours was then quenched in water , and the product was filtered off, washed with water and dried. A recrystallization was not necessary, Pp 72 ⁰ C; Yield 6.6g (pure material).

Example 4

1." 1 -Bis (p-ethoxy phenyl) -2.2-dimethylpropane o

14 g of pivalaldehyde / sodium bisulfite complex became 200 ml of one cooled mixture of concentrated sulfuric acid and acetic acid

_WK 909S8Ü / 1798

«Tar · ssgo. Thereto "orden 15 g of phenol long ·" smgeeetst · As · Reaktlonagemlsch was stirred for 3 hours at 0 to 5 ⁰ C and then poured onto geetoflsene · BII · The Reaktioneprodukt (an oil) vurde by Wiederaueflllung au · a latriumhydroxjdlOvuiig ■ it Saur · cleaned or used without further purification in the near eighth stage, diethyl sulfate was added to 2.6 g of the crude oily product or the pure diphenol compound in 40 μl of a 10% sodium hydroxide solution at room temperature. Naohden The initial exothermic reaction had subsided "was heated, the Löeung at 50 ⁰ C for another 30 minutes. The oil was extracted ■ it ether, and the solid obtained by evaporation of the ether was recrystallized to prepare dae product au · petroleum ether (30 to 60 ⁰ C). Yield 1.6 g; Mp 72 ⁰ C

BelanlelS

Testing the compounds for insecticidal activity ,

(a) house fly »

The following teet procedure was ear determination of the activities

the connections I and also the activities of the others here Listed insecticides used · The tests were conducted by

Drο E, Shipp at the University of New South Wales, N ₀ SoWo, Australia, executed.

House fly tests were done with one sensitive to DDT Standard Stamei (wHO / IH / tousea domestica / 1) If highlighted, then the tests were carried out with resistant to DDT Tribes ("Turramurra" and "Broken Hill") executed. The compounds were injected into an acetone solution through a microinjection needle on the stoop and chest of two-day-olds female flies raised from pupae with a density of 2.2 to 2.5 g / 100 pupae

909884/1798,

was". The adult flies were fed with water and sugar and at 26 ⁰ C and 70 $> relative humidity held the mortalities were paid after treatment 18 hours, and with ace clay-treated en Vergleichßfliegen compared flies that were not capable of "calibrated to move or normal to The LD ^ Q values were obtained from a logit computer program, based on three replicates in 100 flies with each Doeiekon * titration,

(b) Potentiiemngo The compounds Ia and Ib were also tested together with the potentiator "Sesozane" in the above-described insects by applying 5 microliters of a 2 (volume / volume) acetone solution of "Sesoxane" with the compound to be tested, ,

(e) Yellow fever mosquito larvae c. .

These tests were also carried out by Dr. E ₀ Shipp carried out _o

A DDT sensitive strain of Aedes aegypti was used. This strain was grown out of contact with insecticides in a laboratory for several years.Approximately 10 to 25 larvae in the first instar were placed in 10 ml of water together with 100 μl of a suitable concentration of the compound in acetone o The lowest concentration, given in ppm , in the water, which caused complete mortality after 48 hours, was classified as Uß. ₀₀ value taken * In tests in which only acetone was used, there was no mortality "

The results for tests (a), (b) and (c) are in Table II for the compounds Ia and Ib together with equal numbers specified for DDT

909884/1798

1936A94

Insect / trunk

Modomestics . (Sensitive to IKDX) "(with Sesoxane)

Madomeatica (Turramurra)

Modomeatica (Broken Hill)

Ao aegypti

Be is ρ iei toxicity eteata .

Table II units

Ib

¹⁰

IOO

LD ₅₀ (µg / insect) 1.92 2.0 0.26

0.32 0.24

3.20 400

2.60 100

0.32 0.5 0.15

The compound Ia was tested for acute mammalian toxicity in male and female Swiss white mice. The compound was tested intraperitoneally in alkylene glycol (50% solution). The analysis of the mortality data gave an LD ₅₀ at 5200 mg / kg body weight.

example

The following are examples of insecticides according to the invention Compositions indicated. All parts are parts by weight.

909884/1798

(a) Powder dispersible in waaaer " ,

The following powdery composition is suitable for a Dispersion in water to then be used as a spray

will.

Compound of Formula I 5O ₉ O Synthetic fine silica 30.0 Alkylaryl sodium sulfonate 1.5 Methyloellulose (15 op) 0.25 Attapulgite 8.25

fb) Spritaanaatg «,

The following composition is suitable for spray application » Compound of Formula I 4.0

"Sesoxane" 1 * 0

Pyrethrum 0.1

Deodorized kerosene 79.4 Alkylated naphthalene 16.0

(c) aerosol .

The following items will be placed in a suitable bomb-

holder, which is locked in the usual way and is equipped with a valve «

Compound of Formula I 3.0 Methylene chloride 10.0

"Freon 12" 43.0

"Freoa 11" 43.0

Pat entana claims;

90.9884 / 1798

Claims (1)

Claims s Compounds of the general formula I OH ₃ OH ₂ P OCH, GH » where η is equal to 0 or 1. 1,1 -Bis (prfithoxypaenyl) -2,2-dime thy! Propane ί, 1 -Me (p-ethoxyphenyl} ~ 3 $ 3 ~ dimethyl-n ~ butane ₀ Process for the production of veneers of the formula Ha Ha (0H ₂ ) n OE, wherein R is hydrogen, lower alkyl or lower alkoxy *. and in which η is 0 or 1, characterized in that a compound of the formula Hb 909884/1798 lib (CH ₂ ) n
CH ₃ C CH ₃ wherein R and η have the meanings given above * with Sodium reduced in liquid ammonia. 5o method according to claim 4, characterized in that 1 .. ' R athoxy means 6e method according to claim 4 or 5 »characterized in that that the connection of the formula Hb is established by the fact that a Grignard reagent of the general formula -Mg ₀ shark wherein R is as defined above and Hal is bromine or iodine, with a compound of the general formula r »■" '' · ■ '.- ■. ■ -0 ---— (βΗ ₂ ) η - COH wherein η has the above definition and M is a halogen atom or a lower alkoxy group means, reacts » 7 ο Process for the preparation of the compounds of the formula I. and of homologues thereof, characterized in that one 909884/1798 an aldehyde of the formula III (CH ₂ ) n OH »O III where η is 0 or 1, or a reactive derivative same, with a compound of the general formula IV IV wherein R is hydrogen or lower alkyl, in the presence of a catalyst, namely an acid or a Lewis acid, converts o 8 ₀ Process for the preparation of 1, i-bis (p-ethoxyphenyl) -2,2-dimethy! Propane according to Claim 7, characterized in that the product which is obtained by reaction of a sodium bisulfite caplet of a compound of the formula III, in which η equals 0 is with. a compound of the formula IV, in which R "is hydrogen, has been obtained in the presence of a mixture of concentrated sulfuric acid and acetic acid, is ethylated", 9. Process for the production of 1,1-bie (p-athoxyphenyl) -2,2-diaethylpropane according to claim 7, characterized in that a sodium bisulfite complex of a compound of formula III, wherein η is 0, with a compound of formula IV, wherein R "is ethyl, in the presence of a mixture of concentrated Sulfuric acid and acetic acid is converted «, 909884 / 17.98 1O ₀ Process for the preparation of 1, i-bis (p-ethoxyphenyl) -3,3-dlmethyl-n-butane according to Claim 7, characterized in that the product which is obtained by reaction of a sodium lead sulfite complex of a compound of the formula III, in which η is equal to 1 let, a compound of the formula IV in which R ⁿ is hydrogen, has been obtained in the presence of a mixture of concentrated sulfuric acid and acetic acid, is ethylated » 11 ο Process for the preparation of 1,1-bis (p-ethoxyphenyl) -3,3-dimethyl-n-butane according to Claim 7, characterized in that a Hatrumblsulfitkomplex of a compound of the formula III, wherein η is 1, with a compound of formula IV, wherein R "is ethyl, is reacted in the presence of a mixture of concentrated sulfuric acid and acetic acid", 12o insecticidal composition, characterized in that it contains a compound of the formula I «, Oo insecticidal composition, characterized in that it contains a compound of formula II » 14o insecticidal composition according to claim 12 or 1jji _9, characterized in that it additionally contains a synergist or a potentiator _o 15o insecticidal composition according to claim 14, characterized characterized f that the synergist or potentiator is ale inhibitor against an insecticide detergent, which acts through oxidative Bnsyme is called en iso 16 · Insecticidal ZueaMMneetsung according to Anapruoii H, thereby marked that the synergist or potentiator is a 8 8 ^ / 1798 ] * is yrethrin synergist. 17. Insecticidal composition according to claim 14, characterized marked that the potentiator is "Sesoxane *, 18o insecticidal composition according to claim 17 »thereby characterized in that the "Sesoxane" is in an amount of approximately 1/1000 to twice the weight of the compound mentioned is present «, 19 ° insecticidal composition according to claim 18, characterized characterized in that the "Sesoxane" is in an amount of approximately 1/100 up to an equal weight of the named compound is present " 2Oo method for combating insects, characterized in that that the insects are brought into contact with a compound of the general formula I., FATWTANWXITE Dt-We.H.f INCKc, DIPL-ING. H. "OH" DIfL-ING. S. STAEG " 9098 84/1798